Pigments comprising nickel salts of iminoheterocyclicamides

ABSTRACT

HIGHLY COLORED NICKEL SALTS OR CHELATES OF IMINOHETEROCYCLCIC CARBOXAMIDES OR CARBOTHIAMIDES SUITABLE AS PIGMENTS ARE DESCRIBED. THE NICKEL SALTS ARE PREPARED BY REACTING A NICKEL SALT OF A WEAK ACID WITH THE DESIRED IMINOHETEROCYLIC CARBOXAMIDE OR CARBOTHIAMIDE, AS FOR EXAMPLE, WITH 2-IMINOCOUMARIN-3 CARBOXAMIDE, WHICH IN TURN CAN BE PREFORMED OR FORMED IN SITU BY CONDENSING THE APPROPRIATE ALDEHYDE WITH A CYANOACETAMIDE OR CYANOTHIOACAETAMIDE. PIGMENTARY MIXED CHELATES ARE ALSO FORMED IN THE SAME MANNER BY REACTING THE NICKEL SALT WITH A MIXTURE OF THE DESIRED IMINOHETEROCYCLIC CARBOXAMIDE OR CARBOTHIAMIDE AND AT LEAST ONE OTHER CHELATING AGENT SUCH AS, FOR EXAMPLE, DIMETHYLGLYOXIME, 1-NITROSO-2-NAPHTHOL, ETC.

United States Patent ()lfice 3,627,552 Patented Dec. 14, 1971 ABSTRACTOF THE DISCLOSURE Highly colored nickel salts or chelates of iminoheterocyclic carboxamides or carbothiamides suitable as pigments aredescribed. The nickel salts are prepared by reacting a nickel salt of aWeak acid with the desired iminoheterocyclic carboxamide orcarbothiamide, as for example, with 2-iminocoumarin-3-carboxamide, whichin turn can be preformed or formed in situ by condensing the appropriatealdehyde with a cyanoacetamide or cyanothioacetamide. Pigmentary mixedchelates are also formed in the same manner by reacting the nickel saltwith a mixture of the desired iminoheterocyclic carboxamide orcarbothiamide and at least one other chelating agent such as, forexample, dimethylglyoxime, l-nitroso-Z- naphthol, etc.

wherein R is hydrogen, NHalkyl, NHacyl, NHaryl, NHaralkyl, N=CHaryl or aheterocyclic substituted alkyl group; X is oxygen or sulfur; X isoxygen, sulfur, NR or CHR where R is hydrogen or an inert organicradical; Y is oxygen, sulfur, NR or together with X forms a 5-7 memberedring; Z is nitrogen,

O i N or OR where R is hydrogen, hydroxyl or a hydrocarbon group; Z isnitrogen or CR where R is hydrogen, an inert organic or inorganicradical, or together With R forms a 5-7 membered ring; Z is nitrogen orCR where R is hydrogen, hydroxyl, an inert organic radical, or togetherwith R forms a 5-7 membered ring; Z is nitrogen or CR where R ishydrogen, an inert organic radical, or together with X forms a 5-7membered ring; A is an anion; m is 0 or 1; n is 1 or 2; and v is thevalence of anion A, with the further provision that at least one of Z, Zand Z contains carbon.

In the above formulae, R as stated is hydrogen, alkyl, NHalkyl, NHacyl,NHaryl, NHaralkyl, -N:CHaryl or a heterocyclic substituted alkyl group.When R is alkyl or NHalkyl, the alkyl group preferably contains 1 to 20carbon atoms and is, for example, methyl, ethyl, n-propyl, isoproyl,butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl,tetradecyl, hexadecyl, octadecyl, Z-ethylhexyl, 2-cyclohexylethyl andthe like. When R is NHacyl, the acyl group preferably contains 2 to 20carbon atoms and is, for example, acetyl, propionyl, butanoyl,pentanoyl, dec'anoyl, octadecanoyl, benzoyl, phenylacetyl and the like.The aryl groups in -NHaryl, NHaralkyl and N=CHaryl can comprise phenyl,l-naphthyl, Z-n-aphthyl, xylyl, 4-methoxyphenyl and 4- chlorophenylgroups, the aralkyl groups preferably being phenalkyl groups such asbenzyl, phenethyl and the like. The heterocyclic substituted alkylgroups are typically picolyl, methylpicolyl, dimethylpicolyl and thelike.

The inert organic radicals which R R R and R can comprise are numerousand varied and are preferably hydrocarbon or substituted hydrocarbongroups such as alkyl groups containing 1 to 20 carbon atoms, aryl orcycloalkyl groups containing 6 to 18 carbon atoms, aralkyl or alkarylgroups containing 7 to 19 carbon atoms or any of the above groups alsocontaining oxygen, sulfur and/or nitrogen substitutents. Particularlypreferred groups which R can comprise include alkyl, alkoxy, carbamoyl,sulfonamide, alkoxycarbonyl and the like. The hydrocarbon groups which Rcan comprise are preferably alkyl groups containing 1 to 20 carbonatoms, aryl groups containing 6 to 18 carbon atoms, and alkaryl oraralkyl groups containing 7 to 19 carbon atoms. The preferred inertinorganic radicals which R can also comprise include cyano, nitro,trichloromethyl, trifluoromethyl, sulfamoyl, carbamoyl and the like. Aas stated, is an anion of valance v. Preferred anions include halide,alkanoate, thiocyanate, cyanide, sulfate, nitrate, phosphate andhydroxide, and most preferably chloride, bromide, thiocyanate, cyanide,sulfate, nitrate, phosphate, hydroxide, acetate, propionate, 2-ethylhexanoate, octanoate and the like.

The nickel compounds of the present invention are highly colored,insoluble salts which range in color from orange to red to maroon. Thestructure of the nickel compounds, as given above, has not beenestablished unequivocally. However, from the nature of several analogs,it appears that an essential feature of the nickel salt or chelate (assuch salts are often referred to) is a six-membered ring containing 2nitrogen atoms and one nickel atom. Hence, it is postulated that thenickel-containing ring has the structure where, X, R and m are asdefined above. 'It is understood, of course, that the exact hydrogenwhich is replaced by nickel is not known with certainty. It is alsopostulated that the ring adjacent to the nickel-containing ring mustcontain a minimum of one hetero atom which can be nitrogen, oxygen orsulfur, a minimum of 3 carbon atoms, and a conjugated system ofalternating single and double bonds.

Exemplary of compounds represented by Formula I above are the nickelsalts of the Z-imino-ZH- l -pyran-3-carboxamides,

2-imino-2H- l -thiapyran-3 -carboxamides, 1,2-dihydro-2-iminopyridine-3-carboxamides, 1,6-dihydro-6-iminopyridazine-S-carb oxamides,l,6-dihydro-6-iminopyrimidine-5-carboxamides,1,Z-dihydro-2-irninopyrazine-3-carboxamides, 6-imino-6H-l ,Z-oxazine-S-carboxamides, 6-imino-6H- l ,3-oXazine-5-carboxamides,2-imino-2H-1,4-oXazine-3-carboxamides, 6-imino-6H-l,Z-thiazine-S-carboxamides, 6-imino-6H-l ,3-thiazine-S-carboxamides,Z-imino-ZH- l ,4-thiazine-3 -carboxamides,1,6-dihydro-6-iminol,2,4-triazined-carboxamides, l,6-dihydro-6-iminol ,3,4-triazine-5-carb0xamides, 6-imino-6H- l ,2,4-oxadiazine-S-carboxamides, 6-imino-6H- l ,3 ,4-oxadiazine-S-carboxarnides, 6-irnino- 6H-1 ,2,4-thiadiazine-5-carb oxarnides, and 6-imino-6H- 1,3,4-thiadiazine-S-carboxamides,

as Well as the corresponding carbothiamides of the above compounds.Typical compounds represented by Formula II above are the nickel saltsof the 2,5 -dihydro-2-imino-5 -oxofuran- 3-carboxamides, 2,5-dihydro-Z-imino-S-thioxofuran-3-carbox amides,2,5-dihydro-2,5-diiminofuran-3-carboxamides,2,5-dihydro-2-imino-5-substituted iminofuran-3-carboxamides,S-alkylidene-Z,S-dihydro-Z-irninofuran-3-carboxamides,2,S-dihydro-Z-imino-S-oxothiophene-3-carboxamides,2,5-dihydro-2-imino-5-thioxothiophene-3 -carboxamides,2,S-dihydro-2,5-diiminothiophene-3-carboxamides, 2,5-dihydro-2-imino-5-substituded iminothiophene-3-carboxamides, S-alkylidene-2,5-dihydr-2-iminothiophene-3-carboxamides, Z-imino-S -oxo-Apyrroline-3-carbo xamides, Z-imino=-thioXo-A pyrroline-3-carboxamides,2,5-diimino-A pyrroline-3-carboxamides, Z-imino-S-substitutedimino-Mpyrroiine-Zv carboxamides,

S-alkylidene-Z -imino-A pyrroline-3 -carboxamides, 5 -imino-2-oxo-A0xazoline-4-carboxarnides, S-imino-2-thioxo-A oXazoline-4-carboxamides,2,5-diimino-.ir oxazoline-4-carboxamides, S-imino-Z-substituted imino-Athiazoline-4-carboxamides,2-alkylidene-S-imino-Moxazoline-4-carboxamides, 5-imino-2-oxo-Athiazoline-4-carboxamides, 5-imino-2-thioxo-Athiazoline-4-carboXamide-s, 2,5-diimino-A thiazoline-4-carboxarnides,S-iminO-Z-substituted imino-A thiazoline-4-carboxamides,2-alkylidene-5-irnino-A thiazoline-4-carboxamides, 5-imino-2-oXo-Aimidazoline-4-carboxamides, S-imino-Z-thioxo-Aimidazoline-4-carboxamides, 2,5 -diimino-A irnidazoline-4-carboxamides,S-imino-Z-substituted imino-d imidazoline-4-carboxamides, andZ-aIkylidene-S-imino-A imidazoline-4-carboxamides,

as well as the corresponding carbothiamides of the above compounds.

The preferred compounds of the invention include such nickel salts asthose of the Z-imino-ZH-l-benzopyran-S- carboxamides or -carbothiamides(otherwise known as and referred to hereinafter as the2-iminocoumarin-3-carboxamides or-carbothiamides), thel-alkyl-l,2-dihydro-2- iminobenzopyridine-3-carboxamides or-carbothiamidcs (otherwise referred to as thel-alkyl-1,2-dihydro-2-iminoquinoline-El-carboxarnides or-carbothiarnides) and the laryl-l,6-dihydro-6-iminopyridazine-5-carboxamides or -carbothiamides.Particularly preferred are the nickel salts of the2-iminocournarin-3-carboxamides or -carbothia mides having the formulawhere R, R X and m are as indicated above, such as the nickel salts of2-imino-6phenylazocoumarin-3 -carboxamide,7-dimethylamino-2-iminocoumarin-3 -carboxamide,Z-imino-S,6-benzocoumarin-3-carboxamide,Z-imino-6,7-benzocoumarin-3-carboxamide,8-bromo-2-imino-5,6-benzocoumarin-3 -c arboxarnide, 56-benzenesulfonyl-Z-iminocoumarin-3-carboxamide,

and the like, and the 3-carbothiamide analogs of any of the abovecompounds.

Another particularly preferred class are the l-aryl1,6-dihydro-6-irninopyridazine-S-carboxamides or -carbothiamides such as 1,6-dihydro-6-imino-1- (4-nitrophenyl) pyridazine-S- carboxamide,

1- (4-chlorophenyl) -1,6-dihydro-6-iminopyridazine-5- 1 5 carboxamide,

1- 2,4,6-trichlorophenyl 1 ,6-dihydro-6-iminopyrid azine- S-carboxamide,

1- 2,5-dichlorophenyl -1 ,S-dihydro-6-iminopyridazine-5- and thecorresponding carbothiamides, and the 1-alkyl-1,6-dihydro-6-iminopyridazine-5-carboxamides or -carbothiamides such as the1 ,6-dihydro-6imino-1-methylpyridazine-5-carboxamide,

l-ethyll ,6-dihydro-6-iminopyridazine-5-carboxamide,

1,6-dihydro-6-imino-l -propylpyridazine-5-carboxamide,

1-buty1-l ,6-dihydro-6-iminopyridazine-S-carboxamide,

1- (Z-ethylhexyl 1 ,6-dihydro-6-iminopyridazine-5- carboxamide or thecorresponding carbothiamides. The pyridazine ring can also containsubstituents other than those listed above, as for example, keto, ester,amido, sulfonamido or aryl groups, particularly in the 3 position.Typical of such substituents are acetyl, propionyl, benzoyl, cyano,carbamoyl, benzenesulfonyl, ethoxycarbonyl, methoxycarbonyl,phenoxycarbonyl, phenyl, 2,5-dichlorophenyl, 4-methoxyphenyl, sulfamoyland the like.

Still another most preferred class of compounds are the nickel salts ofthe 1,2 dihydro 2 iminoquinoline-3- carboxamides such as, for example,

1,2,-dihyd ro-Z-imino- 1 -methylquinoline-3-carboxamide,

1-ethyl-1,2-dihydro-2-iminoquinoline-3-carboxamide,

1,2-dihydro-2-imino-1 propylquinoline-3-carboxamide,

I-(Z-ethylhexyl) -1,2-dihydro-2-iminoquinoline-3- carboxamide,

l-(benzyl) -1,Z-dihydro-2-iminoquinoline-3-carboxamide,

l, 2,5 -dichlorobenzyl 1 ,Z-dihydro-Z-iminoquinoline- 3-carboxamide,

l-cyclohexyl-t'l ,Q-dihyd ro-2-iminoquinoline-3-carboxamide,

1,2-dihydro-2-imino-1-(4-nitrobenzyl)quinoline-3- carboxamide,

l-carboxymethyl- 1 ,2-dihydro-2-iminoquinoline-3- carboxamide,

1- (2-cyanoethyl -l ,2-dihydro-2-iminoquinolinc-3- carboxamide,

l-carbamoylrnethyl-l,Z-dihydro-2-iminoquinoline-3- carboxamide,

1-(Z-chloroethyl)-1,2-dihydro-2-iminoquinoline-3- carboxamide,

1,Z-dihydro-Z-imino-l-methoxycarbonylmethylquinoline- 3-carboxarnide,

1,2-dihydro-2-imino-1-(3-sulfopropyl)quinoline-3- carboxamide,

1,2-dihydro-2-iminol 2,4-dinitrophenyl) quinoline- 3-carboxamide,

1,2-dihydro-2-iminol 4-sulfamoylphenyl quinoline-3- carboxamide,

1,2-dihydro-2-imino- 1- 4-nitrophenyl quino1ine-3- carboxamide,

1,2-dihydro-2-imino-1-phenylquinoline-3-carboxamide,

1- (2,4-diacetylphenyl -1,2-dihydro-2-iminoquinoline-3- carboxarnide,

4-carboxy-1-methyl-1,2-dihydro-2-iminoquinoline-3- carboxamide,

and the corresponding carbothiamides. Inert substituents can also bepresent in the 5, 6, 7 and 8 positions, the halo,

alkyl, alkoxy and aryl groups being particularly preferred.

The novel compounds of this invention can be prepared by adding asolution of a nickel salt of a weak acid or a solution of a nickelhalide and then a base such as sodium hydroxide, potassium hydroxide,ammonia, triethylamine, sodium carbonate, sodium acetate or the like toan agitated solution or dispersion of the desired iminoheterocycliccarboxamide or carbothiamide in a suitable diluent or solvent usingheat, if desired, and then isolating the nickel precipitate byconventional techniques. Preferred solvents for the nickel salt includewater, methanol, ethanol, 2-methoxyethanol, dimethylformamide and thelike. The diluent for the iminoheterocyclic carboxamide or carbothiamideis preferably the same as that for the nickel salt but can also beacetone, ethyl acetate. benzene, acetonitrile, dioxane and the like.

The nickel salt can also be prepared in a one-step process whereinformation of the iminoheterocyclic carboxamide or carbothiamide (as, forexample, by condensation of the appropriate aldehyde and cyanoacetamideor cyanothioacetamide) and subsequent chelation with the nickel salt arecarried out in the same phase without prior separation. The isolatednickel compounds prepared by either method can be used as such, or canbe purified, as by recrystallization from a suitable solvent, extractionwith a suitable solvent, etc. In the case of nickel compounds of theinvention prepared in aqueous medium, it is preferred to digest theproduct with an organic medium such as dimethylformamide,dimethylsulfoxide and the like to induce crystallinity prior to use.

The iminoheterocyclic carboxamides (or carbothiamides) used to form thenickel salts of this invention can be prepared in various ways. Forexample, the carboxamides of the pyrans and particularly the coumarinscan be prepared by condensing the appropriate aldehyde and particularlysalicylaldehyde with cyanoacetamide or an N-alkyl substitutedcyanoacetamide using the methods of Curtis et al., J. Chem. Soc., 123,3130-40 (1923) or Schiemenz, Ber. 95, 485 (1962). The carbothiamides canalso be prepared in the same manner using cyanothiacetamide or theN-alkyl substituted cyanothiacetamidc. The carboxamides (orcarbothiamides) of the thiopyrans can also be prepared in the samemanner using the thioaldehydes. The carboxamides (or carbothiamides) ofthe pyridines can be prepared by condensing phenylpropargyl- 7 aldehydewith cyanoacetamide or cyanothiacetamide, as the case may be, followedby treatment with a primary amine. The carboxamides of other 6-rnemberednitrogencontaining ring compounds, i.e., the pyrimidines, pyridazines,pyrazines and triazines can be prepared by alkylating the carboxamide orcarbothiamide of the appropriate amino-substituted ring compound with analkyl or aryl halide followed by treatment with a base such as potassiumhydroxide. Carboxamides of the oxazines and thiazines can be prepared byheating an o-aminophenol (or o-aminobenzenethiol) with2-cyano-2,2-bisphenoxyacetamide; and the carboxamides of the oxadiazinesand thiadiazines can be prepared by heating an acylhydrazide (orthioacylhydrazide) with 2-cyano-2,2-bisphenoxyacetamide. Thecarboxamides of the thiazolines and imidazolines can be prepared byheating an N-substituted urea, thiourea or guanidine with2-cyano-2,Z-bisphenoxyacetamide; and the carboxamides of the pyrrolinescan be prepared by condensing an amide of glyoxylic acid withcyanoacetamide. In the above preparations of the carboxamides of theoxazines, thiazines, triazines, oxadiazines, thiadiazines andthioazolines, a final treatment with a base or the use of base insubsequent reaction with the nickel salt may be necessary to facilitatering closure. The carboxamides of the other 5-membered ring compounds,i.e., the dihydrofurans, dihydrothiophenes, and oxazolines can beprepared in similar manner. For example, the carboxamides of thedihydrofurans can be prepared according to the methods of Ito et al.,Tetrahedron Letters, 3659 (1965), the carboxamides of thedihydrothiophenes by the same methods except that the sulfur analogs ofItos carbonyl compounds are used, and the carboxamides of the oxazolinesby heating an alkyl or aryl carbamate with2-cyano-2,Z-bisphenoxyacetamide, followed by treatment with base. Thesubstituted aldehydes can be prepared from the phenol using such knownreactions as the Reimer-Tiemann reaction, the Duff reaction, or theVilsmeier reaction, etc. (see Die Methoden der Organischen Chemie, 4thEd., Sauerstoff II, pages -412, by Houben-Weyl, George Thieme Verlag,Stuttgart, 1954).

The nickel salts of this invention are characterized by being insolublein water and litho varnish and highly colored. They are of value aspigments in numerous applications but have particular value as pigmentsin exterior masstone applications, as for example, in automotivefinishes.

The invention will be illustrated by reference to the following examplesin which all percentages and parts are by weight unless otherwisespecified.

In the examples, the nickel salts were evaluated as pigments 'bypreparing paper drawouts thereof and determining the color visually. Theinks used for the drawouts were prepared by mulling the nickel compoundin litho varnish to form a masstone ink, and then, if desired, reducingthe ink with a white paste, to form a tint ink.

EXAMPLE 1 A solution of 2.4 parts of nickel (II) chloride hexahydrate in3 0 parts of anhydrous methanol was added with stirring to a solution of3.8 parts of Z-iminocoumarin-3-carboxamide (prepared by reacting 10parts of salicylaldehyde with 10 parts of cyanoacetamide in 60 parts ofwater and 1 part of 10% potassium hydroxide and permitting to stand overnight) in 70 parts of warm methanol containing 0.5 part of sodium. Anorange-red solid (97% yield based on the cournarin) which was insolublein benzene, chloroform, ethylene glycol monomethylether, pyridine,dimethylforrnamide, 1:1 benzeneethanol, and water was removed from thesolution by filtration, and extracted once with methanol to remove anyunreacted starting material, Washed with fresh methanol and then driedat C. under vacuum.

The solid product, on analysis for C H N NiO gave:

Found Calculated (percent) (percent) Carbon 55.12 55. 47 Hydrogen 3. 353. 26 Nitrogen (Dumas)..- 12. 71 12.94 Nickel (direct ash)-.- 13.1 13.55

EXAMPLE 2 A mixture of 25.8 parts of Z-hydroxy-l-naphthaldehyde and 12.6parts of cyanoacetamide was dissolved in 300 parts of absolute ethanolby heating on a steam bath, and piperidine (15 drops) was added to thesolution with swirling. The solution was allowed to sit overnight afterwhich time the crystals of 2-imino-5,6-benzocoumarin-3- carboxa-midewhich formed were removed by filtration and washed with absoluteethanol. The crystals recovered above were dissolved in 3,000 parts ofdimethylformamide at C., and a solution of 17.1 parts of nickel acetatetetrahydrate in 300 parts of methanol added with agitation and themixture heated on a steam bath for a few minutes, after which time themixture was cooled and the nickel salt recovered by filtration, washedwith dimethylformamide, then Z-methoxyethanol and finally with methanol,and dried. The nickel salt of 2-imino-5,6- benzocoumarin-S-carboxamide(yield of 82% based on the coumarin) was a red pigment which analyzed9.73% nitrogen (Dumas) and 10.6% nickel by direct ash (calculated for CH N NiO 10.52% nitrogen, and 11.01% nickel). The Inasstone ink (brownishmaroon) and the tint ink (brownish red) both exhibited excellent lightfastness when paper drawouts thereof were exposed in a fadeometer. Thepigment of this example was further evaluated by comparing it in athermosetting acrylic enamel to a blend of equal depth prepared frommolybdate orange and quinacridone violet. (Quinacridones arecommercially useful pigments widely employed in automotive finishe-sbecause of their high degree of light fastness.) Weatherometer andsub-tropical exposures of the panels resulted in less darkeinng in thecase of the pi ment of Example 2 than in the case of the quinacridoneviolet-molybdate orange blend.

EXAMPLES 3 TO 25 In each of these examples, the nickel salts of theinvention were prepared according to the following general procedure.The desired Z-iminocumarin-3-carboxamide which was to be reacted withthe nickel acetate was first prepared by condensing the appropriatealdehyde and cyanoacetamide dissolved in a minimum of anhydrous ethanol,at boiling temperature, it necessary, in the presence of a few drops ofpiperidine and permitting the reaction mixture to stand untilcrystallization was complete, after which time the crystals of theZ-iminocoumarin-3-carboxamide which formed were removed by filtrationand washed with anhydrous ethanol. The nickel salt of the2-iminocoumarin-3-carboxamide was then prepared by dissolivng thecrystals obtained above in a suitable solvent (using heat, ifnecessary), adding nickel acetate tetrahydrate to the solution as asolution in methanol with agitation, and continuing the agitation (usingheat, if necessary) until the desired nickel salt formed. The nickelsalt Was next removed from the reaction medium by filtration orcentrifugation, and the nickel salt washed thoroughly first with thesame solvent as was used for its formation and then with methanol anddried (at 100 C.) under vacuum. Details for these examples and theproducts obtained are tabulated below in Table 1.

TABLE 1 Nickel salt of 2-iminocoumarin-H-carboxamine Ex. Yield,

N0. Aldehyde Solvent 1 Analog percent 2 Formula Color 3 5-methy1salicylaldehyde DMF G-methyl 78 CQzHntNtNiOt O R 4methyl salicylaldehydeM C 7-methyl 84 C H NiNio O S-methyl salicylaldehyde E 8-methyl. 20cnHirNtNio O 6 fi-tert-octyl salicylaldehyde 6-tert-octyk 38 C3 HtN4NiO4 OR 3,5-dimethyl salicylaldehyde 6,8-dimeth yl 80 C241'I22N4N104O 3-tert-buty1-5-methyl salicylaldehyde. 6-methyl-8-tert-octyl. 74 CaoHa|N4N104 O 5-tert-butyl-3-methyl sallcylaldehydeun MCfi-tert-butyl-S-methyl 31 C3cH3-|N4N104 O 5'chloro salicylaldehyde MO6-chloro 54 C2 HitCltNiNiO R -tertbutyl-3 chlor0 salicylaldehyde- MC6-tert-butyl-8-chlor0 78 C28H28C12N4N104 R 3,5-dichloro salicylaldehyde-MC 6,8-dichloro 84 CzoHi ClrNtNiO R 5-brom0 salicylaldehyde MC 71CI'I11B1QN4N104 M 3,5 dibromo salicylaldehy MC 7 C2UI'I1QBI'4N4N104 B R2 DMF 94 C20HHN4N104 O 5 DHF 6-methoxy 64 CEQHIEN4N104 O R 17 4-methoxysalicylaldehyde DMF 7-rnethoxy- 55 c2zH1sN4N1O-i O 19 5-methylthiosalicylaldehyde.w MC 6metl1ylthi 74 C 2H tN NiO S O 2l 5-nitrosalicylaldehyde 47 CzoI'IlQNENlOB O R 23... S-phenylazo salicylaldehyde.70 C32H2zNgNlO4 B R 24..- 4-dimethylamino sallcylaldehydel CriHg N NiOtR 25..." Q-hydroxy-3-naphthaldehyde MC 6,7-benzo 67 C tHrrNtNiOt BAnalyses Percent nitrogen Percent nickel Percent carbon Percent hydrogenDumas) (by direct ash) Ex. No. Theory Found Theory Found Theory FoundTheory Found 1 DMF dimethyliormamide; MC =2-metlioxyethanol; E ethanol;M=methan0l; MC DMF 2-methoxycthanol: dimethyliormamide (2:1)

2 Based on aldehyde.

3 O =orange; R red; O R =orange-red; M =maroon; B R brownish-red; B=brown.

4 Also contained 25.4% chlorine (theory 24.85%). 5 As dimethylglyoxime,using perchloric acid digestion.

EXAMPLE 26 To an aqueous solution containing 1.72 parts of2-hydroxy-l-naphthalclehyde, 0.66 part of 85% potassium hy- Product Awas next ground with Water, filtered, heated with 20 parts ofdimethylformamide at 100 C. for 2 hours and then recovered. This product(designated product B), after drying for 8 hours at 100 C. and 0.55 mm.

dfOXide and 15 Parts of Water Was added a Solution of pressureexhibited, on X-ray analysis, basically the same p cyanoacetarnide in 15parts of Water, and the pattern as the nickel salt of Example 2, thecrystallinity, mixture blanketed with nitrogen- After 2 hours, the ighthowever, being lower with a slight shift in the spacing at yellow solidwas removed from the i u e and s e 7A. Product B contained 10.64%nitrogen (theory, 10.52 with water. The2-imino-5,6-benzocoumarin-3-carboxand 1 92% nickel (theory, 1 01% andgave a amide product (1.62 parts, 68% of theory) contained masstone 1 f11.7% nitrogen (theory, 11.8%) and fluoresced under ultraviolet light.EXAMPLE 27 To a mixture of 0.5 part of the above iminocoumarin Thenickel salt of Example 22 was produced in a one and 0.25 part of nickelchloride hexahydrate ground to a step process by mixing at roomtemperature a solution of fine slurry in 5 parts of water was added 300parts water 55 1.67 parts of 3-nitrosalicylaldehyde and 084 part ofcyand 2 parts of 10% sulfuric acid. The solution which anoacetamide in37 parts 2-methoxyethanol with a soluformed was filtered to removeundissolved solids and then tion of 1.24 parts of nickel acetatetetrahydrate and 1.00 made basic with a solution of 0.53 part of sodiumhydroxpart sodium acetate in 16 parts of methanol, permitting ide in 5parts of water. The nickel salt which formed (desthe mixture to standfor 4 days, and then recovering the ignated product A) was removed fromthe mixture by orange-red solid which formed by filtration and washingfiltration, washed with water and then dried for 7 hours at the solidwith 2-methoxyethanol. To the filtrate (including 100 C. and 0.1 mm.pressure. X-ray analysis of the nickel washings) was added a solution of0.09 part of 85 salt showed little, if any, crystallinity and 3 broaddiffuse potassium hydroxide in 5 parts of 2-meth0xyethanol and, bandsunlike the sharp crystalline lines of the nickel salt after permittingto set for 1 day, a second crop of solid of Example 2. was filtered offand washed with methanol. Third and fourth crops of solid were recoveredin the same manner as above except that a methanolic solution ofpotassium hydroxide was used and the mixtures permitted to stand for 5days and 8 days respectively prior to filtration. The fourth crop afterdrying for 5 hours at room temperature and 0.15 mm. pressure was foundto contain 14.64% nitrogen (theory, 15.03%) and 11.2% nickel (theory,10.50%

EXAMPLE 28 A mixture of 3.76 parts of 2-iminocoumarin-3-carboxamide and2.00 parts of hydroxylamine hydrochloride in 12 EXAMPLES 29 to 32 TABLE2 Nickel salt Analyses Precent Percent Percent nitrogen Percent nickelcarbon hydrogen (Dumas) (direct ash) Example 501- Yield, Color, numbervent percent 2 Formula Theory Found Theory Found Theory Found TheoryFound masstone 88 C32H24N5N104 62. 47 62. 6 3. 93 4. 13. 66 13. 74 9. 549. 1 Brown. 57 C34H24NsNiO4 63. 88 64. 37 3. 78 4. 25 13. 15 13. 55 9.18 5. 67 Red. 95 CasHmNeNiOa 52. 68 52. 44 3. 68 4. 24 15. 36 15. 01 10.73 10. 22 Brown. 74 G23H24NBN104.2H20 59. O1 58. 91 4. 33 4. 36 12. 9113. 31 9. 01 9. Red-brown.

1 MC=2-methoxyethanol; M=methanol. 2 Based on iminocoulnarin.

100 parts of 95% ethanol was stirred mechanically for EXAMPLE 33 severalhours and the mixture allowed to stand overnight, after which time thesolid was removed by filtration. The filtrate was next reduced involume, and a second crop of solid was recovered as above. The two cropsof solid were combined and recrystallized from 95% ethanol, giving 2.3parts of a yellow, crystalline solid which was identified as2-oximinocoumarin-3-carboxamide [decomposed at 260 C. without definitelymelting and contained on analysis for C H N O 59.50% carbon (theory,58.82 3.97% hydrogen (theory, 3.95%) and 13.31% nitrogen (theory,13.72%)1.

To a solution of 1.70 parts of the 2-oximinocoumarin- 3-carboxamideobtained above in 150 parts of boiling methanol was added a solution of1.04 parts of nickel acetate tetrahydrate in 50 parts of methanolfollowed by a solution of 0.55 part of 85% potassium hydroxide in 50parts of methanol. The mixture was next filtered to remove a trace ofbrown impurity, the filtrate reduced in volume by distilling off most ofthe solvent, and the run stored at 0-5 C. After several days, the nickelsalt which had formed was removed by filtration and washed withmethanol. The orange-brown product yield based TAB LE 3.MIXED Theprocedure of Example 3 was repeated except that salicylaldehyde wascondensed with cyanothioacetamide. The nickel salt was a brownish-redpigment which analyzed 11.6% nitrogen (Kjeldahl), 12.07% nickel and13.6% sulfur (calculated for C H N NiO S 12.05% nitrogen, 12.62% nickeland 13.78% sulfur).

EXAMPLES 34 to 38 Mixed nickel salts of Z-iminocoumarin-3-carboxarnidewere prepared by adding a soltion of a mixture of the 2-iminocoum'arin-3-carboxamide prepared in Example 1 or the 5,6-benzoanalog prepared in Example 2 and various second chelating agents in asolvent to a solution of the calculated amount of nickel acetatetetrahydrate in methanol. The solid which formed was filtered off,washed with methanol and dried for several hours at 100 C. under 0.1 mm.pressure. The mixed salt formation was established by X-ray analysis, ascompared with analyses for the individual salts. Details for theseexamples and analyses for and evaluation of the products obtained aregiven in Table 3 below.

NICKEL SALTS Analyses 3 Yield N iC-kel Example S0l (per- Hydro- Nitrogen(direct Color, Number Chelating agents vent 1 cent) Formula Carbon gen(Dumas) ash) Masstone 34 2-iruinocoinnarin-3-carbexamine and di- M 88cuHuNiNiOi 46.1 (46. 6) 3.9 (3.9) 15.7 (15.5) 15.9 (16. 3)Brownishmethylglyoxime. red. 35 2-irninocoumarin-3-carboxamide and 1- M88 C2oH11N5N1O 51.5 (51.6) 4.0 (3.7) 15.0 (15.0) 12.3 (12.6) Deep red.

aniline l ,2,3-butanetrione-2,3-dioxirne. 362-irninocoumarin-3-carboxamide and 1- MC 75 CZuHlsNJNlO; 56.9 (57.5) 3.3(3.1) 10.1 (10.1) 13.9 (14.0) Charcoal nitroso -2-naphthol. gray. 372-irninocoumarin-3-carboxamide and 2- MC 87 C23Hi1N NiO3 14.6 (14.9)12.5 (12.5) Dark red.

(2-lrydroxy-5-methylphenyl)-benzotriazo e. 382-imin0-5,6b-enzocoumarin-3-carbox- DMF 92 C1BH10N4N104 13.8 (13.6) 14.1(14. 3) Deep red.

amide. and dirnethylglyoximed 1 M =methan0l; MC =2-methoxyethanol; D MFdimethylformamide.

2 Based on iminoeqmnarin. V 3 Percent; theory given in parenthesesfollowing figure.

EXAMPLES 39 to 59 Other nickel salts of the invention were prepared byreacting a methanolic solution of the calculated amount (for a 1:2 salt)of nickel acetate tetrahydrate With various imino heterocycliccarboxamides in a suitable solvent according to the general procedure ofExample 2. Details of these examples and the pigmentary nickel saltsobtained are given below in Table 4.

23 What I claim and desire to protect by Letters Patent is: 1. A pigmentcomposition comprising a nickel salt having a formula selected from thegroup consisting of gen or CR where R is hydrogen, hydroxyi, an inertorganic radical or together with R forms a 5-7 membered ring; Z isnitrogen or CR where R is hydrogen, an inert organic radical or togetherwith X forms a 57 membered ring; A is an anion; m is 0 or I; n is 1 or2; and v is the valence of anion A, with the further provision that atleast one of Z, Z and Z contains carbon and a pigment vehicle selectedfrom the group consisting of inks and enamels.

2. The composition of claim 1 wherein the nickel salt has the formulawhere R, R X, A, n, m and v are as indicated in claim 1.

3. The composition of claim 2 wherein the nickel salt is. the nickelsalt of Z-imino-5,6-benzocoumarin-3-carboxamide.

4. The composition of claim 2 wherein the nickel salt is the nickel saltof Z-irnino-6-tert-octylcoumarin-3-carboxamide.

No references cited.

TOBIAS E. LEVOW, Primary Examiner J. V. HOWARD, Assistant Examiner US.Cl. X.R.

@53 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTTON Patent3,627,552 Date December 14, 1971 Inventor(s) Albert S. Matlack (Case27-28) It is certified that error appears in the above-identified patentand that said Letters Patent are hereby corrected as shown below;

In the formula I, Column 1 far right side of second bracket: N2A2 shouldread "'NiA2 5 Column l, printed line 15; (line 4 of abstract) "nickelsalt" should read --a nickel halide or a nickel salt-- Column 4, line 6;"thiazoline" should read oxazoline Column 5 printed line 18; "1,5"should read l,6--

Column 10, Table 1 under Column entitled Formula, Exp. l5,

l6, l7, and 18;

"NiO should read -NiO Column 10, Table 1, 2nd Section under last columnentitled Found, Exp. 13;

"9.17" should read -9.7--

Column 10, line 54;

"0.55" should read 0 .O5--

Column ll, Table 2, Exp. 31 in the column entitled Formula;

"C34" should read -C24 Column ll, Table 2, Exp. 32 in the columnentitled Formula;

L C23 should read C32 P0405) UNITED STATES PATENT OFFICE CERTIFICATE OFCORRECTION Patent No. 3 627 552 Dated December 14 1971 Inventor(s)Albert ,S. Matlack (Case 27-28) Paqe 2 It is certified that errorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown below:

Column ll, Table 3, Exp. 34, second column;

"3-carboxamine" should read 3carboxamide Column 11, Table 3, Exp. 38,second column;

"5,6b-enzocoumarin" should read -5,6benzocoumarin Column 17, formula inExp. 50:

P0405) UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3 627 552 Dated December 14 197 l Inventor(s) Albert S. Matlack (Case27-28) Page 3 It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

Claim 2, Column 24 in the formula,-

l I d NHR NIA l7 2 should read 4 mm 2 \1 NiA Signed and sealed this 6thday of June 1972.

(SEAL) lamest: J

EDWARD M.FLETCHER, JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents

